Imidazolidinethiones



Patented Oct. 7, 1952 UNI-TBI), PATENT OFFICE ...vs IMiDlripLrnrNeTHroNEs' oiellvm D. Hrwiraruilauelphia,'and noten w. f"

Auten, Jenkintown, Pa., assignors 'to Rohm & Haas Company, Philadelphia, Pa., 'a .corpora-` tion of Delaware No or-swing. Application october carota j serial No. leasen y.

c creams. (c1. attesta?) This invention concerns 2-in1idazoli-dinethi' onec'fhaving on a ring nitrogen an aminoethyl grouping. This invention `also `deals withl a process by which these compounds are prepared.'l

According to this process la dfi-alkylenetriamine- "i having' a chain of two carbon 'atoms between nitrogens is reacted `with.'carl'nin bisulde' with elimination of hydrognsuliide by heating the two reactants together 'at temperatures from 30 to 250 C. The reaction is usually initiated at 0 to 50 C. and continued bylraising the temperature above 200 C. thus completing the reaction and ensuring elimination of hydrogen sulfide and any other volatile products. Suc-h temperatures also cause decomposition of thiooarbamates and like compounds which may formas intermediates.

The amines which can be thus reacted with carbon bisulde are diethylenetriamine, dipropylenetriamine, and the N-methyl derivatives thereof. These di-1,2-alkyl-enetriamines may be summarized by the formula i nNH-oH-CH-NH-CH-CHNHZ Il?! RHI Rllll where the various R substituents represent -hydrogen or the methyl group with the proviso that at least one member of the pair R' and R" and of the pair R" and Rm is hydrogen.

The following examples supply more details of typical preparations of imdazolidinethiones according to the process of th-is invention.

Example 1 Soon decomposition became rapid and steam was passed through the condenser jacket to prevent clogging. The hydrogen sulde evolved was hushed with la Water jet. As the temperature of the reaction mixture was increased, there were changes in color from la clear yellow .at 110 to a light green -at 120 toa deep blue-green at 165 to a light yellow at 180 C. Heating was discontinued lat 200210 C. Color changes in reverse from the took place when the reaction mixture was cooled. At 96 C. it solidified. The

produce was taken up sy acetic-git wanton parts-oiethanol containing benzene. 'Jlh'eisoliu tion was ltered and crystals were obtained. The main fnactionlamounted to 610 parts melting at 111112 C. An additional 106 parts of'product was obtained from the motlrerr-liquor.v The cornloined products melted at 1l0112 C. Iand had a neutral equivalent of 1&5. This was an 82% yield Example 2 S il where one of each pair of RX-R and RX"- R" is methyl and the other hydrogen. The product appears to be a mixture of isomers.

Example 3 There was placed in the reaction vessel 11T parts of N-(beta-methylaminoethyl) ethylenediamine and 75 parts of carbon bisulde was slowly added and mixed therewith. These materials reacted and were heated, the excess carbon bisuliide being distilled out and the temperature of the reaction mixture being carried to over 200 C.

`and then cooled. The product was washed with alcohol and a crystalline solid obtained which contained 20.3% of sulfur and 26.3% of nitrogen, corresponding in composition to Nmethyl-N- beta aminoethyl 2 imidazolidlnethione, for

lwhich theoretical values are 20.1% and 26.4% for sulfur and nitrogen respectively. This compound may also be called 1-methyl-3-beta-'aminoethyl- 2-imidazolidinethione- 3 The beta. aminoethyl-2imidazolidinethiones, which may be represented by the formula S Il CH--CH-NHa can be reacted with thiourea or urea to give thioureidoor ureido-ethyl derivatives, when an above compound and thiourea or urea are heated together up to about 200-250 C. or more in equimolar proportions. When two moles of one of the above compounds is thus heated with a mole of thiourea or urea, there results a. bis- (thionoimidazolidylethyl) thiourea or urea. y

These various compounds react with formwhich comprises reacting together carbon bisul- V l ll lll/ 4 and heating the reaction mixture to a. temperature between 200 and 250 C., in the above formula the R substituents representing at least one member of the class consisting of hydrogen and the methyl group with the requirement that of the pair R' and R" and of the pair R'" and R" atleast one of the substituents is hydrogen.

2. A process for preparing N-beta-aminoethyl- Z-imidazolidinethione which comprises reacting together carbon bisulde and diethylenetriamine and heating the reaction mixture to a temperature between 200 and 250 C.

3. As new chemical substances, compounds of the formula s l o wherein the R substituents represent members of the class consisting of hydrogen and the methyl group with the requirement that of the pair R and R" and of the pair R'" and R at least one of the substituents is hydrogen.

4. As a new chemical compound, l-(betaaminoethyl) -Z-imidazolidinethione.

MELVIN D. HURWITZ. ROBERT W. AUTEN.

No references cited. 

1. A PROCESS FOR PREPARING IMIDAZOLIDINETHIONES WHICH COMPRISES REACTING TOGETHER CARCON BISULFIDE AND AN AMINE OF THE FORMULA
 3. AS NEW CHEMICAL SUBSTANCES, COMPOUNDS OF THE FORMULA 